Stabilization process for color photographic materials

ABSTRACT

The physical properties and storage stability of color photographic papers are improved by processing them in a stabilization bath containing a water-soluble zirconium salt and a polycarboxylic acid.

United States Patent Iwano et al.

STABILIZATION PROCESS FOR COLOR PHOTOGRAPHIC MATERIALS Inventors: Haruhiko Iwano; Kazuo Shirasu;

Tadao Hatano, all of Minamiashigara, Japan Assignee: Fuji Photo Film Co., Ltd.,

Minami-ashigara, Japan Filed: Dec 13, 1973 Appl. No.: 424,253

Foreign Application Priority Data Dec. 13, 1972 Japan 47-124915 US. Cl. 96/56; 96/22; 96/11 1 Int. Cl. 003C 7/00 Field of Search 96/56, 111, 22

[56] References Cited UNITED STATES PATENTS 2,657,139 10/1953 Bates 96/56 3,140,177 7/1964 Welch 96/56 3,424,580 1/1969 Wainer .1 96/33 3,582,347 6/1971 Holly at al. 96/111 3,666,468 5/1972 Amano et al. 96/56 3,676,136 7/1972 Mowrey 96/56 Primary E.\'aminerJ. Travis Brown Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT The physical properties and storage stability of color photographic papers are improved by processing them in a stabilization bath containing a water-soluble zirconium salt and a polycarboxylic acid.

11 Claims, N0 Drawings STABILIZATION PROCESS FOR COLOR PHOTOGRAPI-IIC MATERIALS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilization pro cess for color photographic materials and, more particularly, it relates to a process for improving the physical properties of color photographic materials and the storage stability of color photographic images.

. 2. Description of Prior Art It is known that the stabilization bath used in the processing of photographic light-sensitive materials has a very important relation to the stability of the images of the photographic material and various studies have been made on stabilization. For instance, as disclosed in the specification of US. Pat. No. 2,788,274, the fadingof color images of color photographic materials can be effectively prevented by processing the color photographic materials with an aqueous solution of a zinc compound. Howeventhis process is not effective for preventing the formation of stains due to the action of light and heat.

Also, it is known to add a polycarboxylic acid to a stabilization bath as described in the specification of British Patent No. 736,881, The British Journal of Photography; July 8, 1966, pages 588-589, and ibid.; Sept. 27, 1968, pages 838-840. By this process the image stability can be improved with an increase in the content of the polycarboxylic acid but the physical properties of the photographic material are degraded with the increase of the content of the polyearboxylic acid and, hence, the process has a demerit in that it does not satisfy simultaneously improvement in the image stability and the physical properties of photographic materials.

On the other hand, it is known that a stabilization bath containing a watersoluble aluminum salt and a polycarboxylic acid can improve simultaneously the image stability and physical properties of photographic materials as described in US. Pat. 3,666,468 but the improvement by the process is not satisfactory.

The reaction of physical properties of photographic materials after processing includes the following various matters.

Photographic papers which have been subjected to photographic processingare usually stored by mounting them on a pasteboard mat or in an album having a transparent film cover or by placing them directly in a bag or box. The temperature and humidity in the storage of the processed photographic papers depend on the season, the climate, and the location but in any case, if the storage conditions are at low temperature and low humidity, physical difficulties such as adhesion or stickiness is less and they increase as the temperature and humidity increases. For instance, when color prints obtained by the known processes as described in the abovementioned The British Journal of Photography; July 8, 1966, pages 588589, ibid., Sept. 27,-1968, pages 838-840, and the specifications of British Pat. No. 736,881, and US. Pat. No. 3,666,468 are preserved under a high-humidity conditions, the following difficulties tend to occur:

1. When the photographs are mounted on both sides of the mats of a usual album. the photographs which are brought into contact stick each other.

2. Whenthe photographs are mounted on a mat of an album having a transparent cover film on the mat, Ne-

tons rings are formed or dissolved matter in the cover film, such as plasticizers, causes sticking.

3. When the photographs are stacked together in a bag or box, they stick to each other.

4. In any of these cases, the surface of the photographs becomes sticky, fingerprints are left thereon or dust sticks thereto making the images dull.

Also, it is well known that electrostatic charges are frequently formed in an ordinary processing step, in particular the drying step for photographic papers, and if such electrostatic charges are formed on photographic papers, the stacked photographic papers after cutting will be disordered or the photographic papers will stick to each other complicating counting or checking them.

Furthermore, the steps for processing photographic papers having a baryta-coated paper as the support include a drying step using a ferrotype dryer. ln particular, in drying color photographic papers using a ferrotype dryer, the hardening bath and stabilization bath becomes frequently questions since they are subjected to various processings before drying. For instance, when the color photographic paper processed in the manner as described in The British Journal of Photography, Sept. 27, 1968, pages 838840 and the specification of British Pat. No. 736,881 is subjected, as it is, to high-temperature high-speed ferrotype drying, the photographic paper sticks to the ferrotype plate. Such inconvenience is considerably improved by using, in drying a rolled photographic paper, the predryer and the re-wetting means as described in Kodak Products for V the Professional, page 6977 (1968) but this attempt has the disadvantage that the aforesaid means additionally is required. Other attempts have been proposed on techniques for polishing the ferrotype plate and on various processing compositions but those attempts have also the defect that they are quite troublesome.

On the other hand, it is known that a photographic material itself or a processing bath gets musty under certain conditions and various attempts have been made for preventing the materials from getting musty. For instance, such attempts are the processes as described in Photographic Science and Engineering, 3, 3,132 (1959) and the specification of US. Pat. No. 3,093,479.

SUMMARY OF THE INVENTION An object of this invention is, therefore, to provide a stabilization process for color photographic materials for improving the physical properties of the color photographic materials.

Another object of this invention is to provide a stabilization process for improving the storage stability of color photographic images.

Still another object of this invention is to provide a processing bath for color photographic materials for improving the above-mentioned physical properties and storage stability, in which the bath itself is also quite stable.

The aforesaid object of this invention can be attained by processing color photographic materials with a processing bath containing a water-soluble zirconium salt and a polycarboxylic acid.

That is to say, the present invention provides a process of processing color photographic materials which comprises processing color photographic materials with a bath containing a water-soluble zirconium salt and a polycarboxylic acid.

DETAILED DESCRIPTION OF THE INVENTION Suitable water-soluble zirconium salts which can be used in this invention, are zirconium salts such as zirconium sulfate, zirconium nitrate, zirconium chloride, zirconium oxysulfate, zirconium oxynitrate, and zirconium oxychloride. Of these zirconium salts as illus trated above, zirconium oxysulfate is particularly effective. The zirconium salts can be used individually or as a mixture of two or more salts and the amount of the zirconium salt generally used 1 to g/liter, preferably 2 to 6 g/liter.

Also, suitable polycarboxylic acids which can be used in this invention are acids such as oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, citric acid, glutaric acid, adipic acid, lactic acid, crotonic acid, aconitic acid, itaconic acid, diglycolic acid, and citraconic acid and the salts of these acids, such as the alkali metal salts, e.g., the sodium and potassium salts, ammonium salts, etc. Suitable polycarboxylic acids which can be used in this invention are disclosed, for example, in U.S. Pat. Nos. 2,515,121; 2,518,686; 3,140,177; 3,582,332; and 3,676,136. The polycarboxylic acids or the salts thereof can be used individually or as a mixture of them and the amount of the polycarboxylic acid generally used 1 to 15 g/liter, preferably 2 to 10 g/litcr.

It is well known that a polycarboxylic acid acts as a buffer for a stabilization bath but the feature of this invention is in the point that an even higher buffer action is obtained using the polycarboxylic acid together with the zirconium salt.

The stabilization bath of this invention is used at a pH of 2.7 to 4.5, preferably 3.3 to 4.0. The pH of the stabilization bath of this invention can be adjusted using an alkali such as sodium hydroxide, sodium metaboratc, borax, amine, etc.,'or an acid such as boric acid, acetic acid, sulfuric acid, etc., as disclosed in U.S. Pat. Nos. 2,515,121; 2,518,686; 3,140,177; 3,582,322, 3,676,136 and 2,647,057.

Another manner of using a zirconium salt which is different from the present invention is in a hardening bath containing a zirconium salt as disclosed in the specification of British Pat. No. 1,271,025. However, although such a known bath may be effective for hardening during processing, the bath is not effective for improving the image stability and the physical properties of photographic materials after processing and hence it is clear that this is different from the process of this invention is effect and the manner of using.

On the other hand, the objects of this invention as described before are not attained by using a bath containing a zirconium salt or a zirconium salt and an aldehyde. In other words, the objects of this invention are attained by processing color photographic papers with a bath containing simultaneously a water-soluble zirconium salt and a polycarboxylic acid or a salt thereof, with the pH of the bath having been adjusted to 2.7 to 4.5, as a final step in the color process for the color photographic papers.

The processing bath of this invention containing the water-soluble zirconium salt and the polycarboxylic acid or a salt thereof can further contain at least one of a compound having an aldehyde group and a compound capable of forming formaldehyde.

wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a carboxyl group, or a heterocyclic ring residue, said'R may have been sub stituted, and when R is a hydrogen atom, n represents an integer and when R is a substituent other than a hydrogen atom, n is l.

Specific examples of compounds represented by the general formula (I) are formaldehyde, paraformaldehyde, acetaldehyde, aldol, propionaldehyde, acrolein, crotonaldehyde, salicylaldehyde, glyoxylic acid, muco,-. chloric acid, mucobromic acid, furfural, diglycolaldehyde, etc. Also, precursors of compound of the general formula (I) can be used as the water-soluble compound having an aldehyde group.

Also, as the compound having an aldehyde group, the dialdehyde compounds represented by the general formula (II) can be used.

one (R Cl-IO wherein R represents a divalent aliphatic residue or a divalent aromatic residue, and m is O or 1.

Specific examples of compounds represented by the general for-mula (II) are glyoxal, succinaldehyde, glutaraldehyde,, a-methylglutaraldehyde, cyclopentane; dicarboxyaldehyde and the dialdehydes described in the specification ofBritish Pat. No. 1,102,001, e.g.,

CH CH0 CH CHO O and HN CHz CHO caz CH0 and in the specification of U.S. Pat. No. 3,565,632,

CHO one-g OH R CH Ol-I (III) wherein R represents an aliphatic group, an aromatic group, or a heterocyclic ring residue.

Examples .of compounds represented by the general formula (III) and the Nmethylol compounds are ,N- methylolurea, thylenebismonoethylurea,

N,N-dimethylolurea,' N-rnethylolme N-methylol-N,N- I dimethylolurea, methylolhydantoin, hydroxydimethylbiuret, trihydroxymethylbiuret, 2,2,6,6-tetramethyloleyclohexanol, methylol dicyandiamide, the compounds described in the specification of British Pat. No. 1,1 16,944 (such as 3-hydroxy-2,Z-dihydroxymethylpropionic acid), the 2-nitroethanol derivatives described in the specification of British Pat. No. 1,258,359 (such as 2-nitro-2-methyl-l,3-propanediol, and N-hydroxymethylmorpholine).

- Suitable examples of aldehydes which can be used in the stabilizing bath are disclosed in US Pat. Nos, 2,518,686 and 3,140,177.

The water-soluble aldehyde compound or the compound capable of forming formaldehyde as described above can be used in an amount sufficient'to attain the objects of this invention but the amount of the aldehyde compound generally used is about 1.2 X to 1.8 X 10 mol/liter, preferably 4.2 X 10 to 1.1 X 10 mol/liter and the amount of the compound forming formaldehyde generally used is 1.0 X10 to 1.7 X 10, preferably 4.1 X 10 to 1.2 X 10 mol/liter. Of the aldehyde compounds described above, in using the dialdehyde compounds better results can be obtained by using it in an amount of 1.0 X 10' to 1.7 X 10" mol/litcr.

On the other hand, a method of improving the stability of a magenta image by processing a photographic material containing a pyrazolone coupler with a stabilization bath containing a polycarboxylic acid and an aldehyde is known as disclosed in the specification US. Pat. No. 3,140,177. However, although the method may be excellent in image stability, when the polycarboxylic acid and the aldehyde are used in the amounts disclosed in the specification of this US. patent, the photographic materials thus processed are greatly reduced in physical properties. In particular, when the amount of the aldehyde is increased, the physical prop erties of the processed photographic material are greatly degraded and the use of these compounds is unpleasant because'of their irritative smell. Further stains are readily formed depending on the storage conditions. Hence, the objects of this invention can not be attained using such a known method.

The processing bath of this invention containing the water-soluble zirconium salt and the polycarboxylic acid or a salt thereof can further contain a water? soluble organic acid such as benzoic acid or an alkali metal salt of benzoic acid. A suitable level of use ranges from about 0.01 to 10 g/l, preferably 0.1 to 1 g/l, for the benzoic acid or its alkali metal salt.

It is desired that the stabilization bath of this invention be used fundamentally after finishing the develop ment steps of color photographic materials, that is to say, after finishing the development, bleaching, and fixing. After processing with the stabilization bath of this invention, the photographic material can be rinsed.

The development steps for color photographic materials which are employed prior to the use of the stabili zation bath of this invention can be conventional color processes for color photographic materials as disclosed in US. Pat. Nos. 2,515,121; 2,518,686; 2,647,057; 3,140,177; 3,582,322 and 3,676,136. The steps include basically the steps of development, bleaching, and fixing as described in, e.g., the publications as described above. Of course, other embodiments of development steps including a blix step or a stopfix step can be employed. Also, any of these steps in the development can be followed by a wash step or another step.

The stabilization process of this invention can be applied to any color photographic materials but it is preferably applied to color photographic paper which have photographic emulsions containing at least one 4- equivalent or Z-equivalent coupler.

Examples of 4-equivalent couplers are shown below:

Namely, the pyrazolone couplers giving a magenta dye represented by the following general formula are particularly useful.

wherein R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group and R represents an alkyl group, a carbamyl group, an amino group, or an amide group.

Specific examples of the 4-equivalent couplers represented by the above formula are:

1-p-sec-amylphenyl-3-n-amyl-5-pyrazolone,

2-cyanoacetyl-5-(p-sec-amylbenzoylamino)cumarone,

2-cyanoacetylcumarone-5(N-n-amyl-p-tamylsulfoanilide), 2-cyanoacetylcumarone-5-sulfon-N-n-butylanilide, 1-p--laurylpheny1-3-methyl-5-pyrazolone, 1-,8-naphthyl-3-amyl-5-pyrazolone-1-p-nitrophenyl- 3-n-amyl-5-pyrazolone, 1-phenyl-3-acetylamino-5-pyrazolone, 1-phenyl-3-n-vareamino-5-pyrazolone, l-phenyl-3-chloroacetylaminoS-pyrazolone, 1-phenyl-3-( m-aminobenzoyl )amino-S-pyrazolone, 1-p-phenoxyphenyl-3-(p-t-amy1oxybenzoyl )amino-S- pyrazolone, l-(2,4',6'-trichlorophenyl)3-benzamido-5- pyrazolone, 1-(2',4-dich1orophenyl)-3-[3(2",

amylphenoxyacetamido)benzamido]-5- pyrazolone, and l-(2,4-dimethyl-6-chlorophenyl)-3-[3-(2",4"'-ditamylphenoxyacetamido)benzimido]-5- pyrazolone.

Suitable examples of pyrazolones which are suitable are disclosed, for example, in US. Pat. No. 3,582,322.

Also, the 4-equivalent couplers as disclosed in the specifications of US. Pat. No. 3,558,319, British Pat. No. 1,142,553, US. Pat. No. 3,337,344 and Japanese Pat. publication No. 20,636/1970 can be used for the color photographic papers stabilized by the process of this invention.

Furthermore, the 4-equivalent couplers giving benzoylacetanilide type yellow dyes or pivaloylacetanilide type yellow dyes are described in the specifications of British Pat. No. 1,113,038; US. Pat. No. 3,551,156; US. Pat. No. 3,337,344; Japanese Pat. publication No. 19,956/1970; and US. Pat. application, Ser. No. 319,806, filed Dec. 29, 1972. Specific examples of the 4-equivalent couplers are:

a-{3-[a-(m-pentadecylphenoxy)butylamido]benzoyl}-2-chloroacetoanilide,

a-{3-[a-(2,4-di-tamylphenoxy )butylamido lbenzoyl }-2- methoxyacetanilide, a-{3[oz-(2,4-di-t-amylphenoxy)butylamido]benzoyl }-2-chloroacetanilide, 2-chloro-3-[2,4-di-t-amylphenoxy)butylamidolbenzoylacetanilide, a-{3[a-(2,4-di-t-amylphenoxy)acetamido]benzoyl} benzoylacetanilidc, and apivalyl-2,5-dichloro-4-[N-(n-octadecyl)-N- methylsulfamyl]-acetanilide.

The 2-equivalent couplers as disclosed in the specifications of US. Pat. No. 3,582,322 can be used as couplers for color photographic papers processed by the process of this invention. Also, the phenolic couplers giving cyan dyes as disclosed in the specifications of U.S. Pat. No. 2,423,730 and US. Pat. No. 2,801,171 can be effectively used.

The color photographic emulsions for the color photographic materials processed by the process of this invention are those prepared by dispersing a silver halide such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide, etc., in a natural or synthetic water-soluble polymer such as gelatin, gelatin derivative (e.g., phthalated gelatin, malonated gelatin, etc.,), colloidal albumin, cellu lose derivatives, etc., for example, as disclosed in US. Pat. No. 3,582,322.

These silver halide photographic emulsions can contain, in addition to the aforesaid couplers, conventional additives well known in the photographic art, such as dye sensitizers, antifoggants, stabilizers, hardening agents, coating aids, etc., as desclosed in US. Pat. No. 3,582,322.

The silver halide emulsion as described above is coated on conventional support such as a barytacoated paper, a polymer-coated paper such as polyolefin coated paper (as disclosed in, eg, the specifications of Japanese Pat. publication No. 19,164/1968 and British Pat. Nos. 1,314,196 and 1,134,197), and a so-called synthetic paper prepared by making opaque a transparent film of a polymer such as polyolefin, cellulose derivative, etc. Furthermore, when the process of this invention is applied to, in particular, color photographic papers, excellent advantages are obtained.

By the process of this invention the following excellent results are obtained.

1. When photographs processed by the process of this invention are stored in an album for a long period of time under various conditions, neither adhesion nor stickiness is observed.

2. The generation'of static charges caused by the friction of the photographs with rollers which are brought into contact with the photographs during the processing and drying steps or with the ferrotype plate is greatly reduced.

3. Images having excellent stability to light are obtained.

4. When the photographs are stored for a long period of time without exposure to light, the stability of the images of the photographs is not degraded.

Moreover, when a baryta-coated paper is used as the support for the photographic paper, the following specific effects are obtained.

1. At ferrotype drying, the photographs do not stick to the ferrotype plate.

2. A predryer required in ferrotype drying in the conventional case becomes unnecessary.

Also, the stabilization bath used in this invention has the following advantages:

1. The stabilization bath does not get musty.

2. The stabilization bath has a higher buffer action.

An extremely important advantage of the color photographic paper processed by the stabilization process of this invention is that the photographic paper shows excellent physical properties when the photograph is stored under various conditions and additionally photographs processed by the stabilization process of this invention have stable images as described above is also an excellent advantage of this invention. That is to say, according to the process of this invention, a color photograph having not only a stable magenta color image but also cyan and yellow color images is obtained. Also, when the photographic papers are preserved under various conditions, less formation of stains is observed. The image stability of the photograph processed by the stabilization process of this invention is particularly excellent when the photograph is exposed to hightemperature and high-humidity conditions and also to light. The effects or advantages of this invention are confirmed by referring to the method of Photographic Science and Engineering; 1 l, (5), 295-305 (1967).

Also, by the process of this invention, electrostatic charges are formed on the photographic paper to a lesser extent and thus the occurrence of difficulties caused by the formation of static charges can be prevented.

By processing a color photographic paper after color developing, stop-fixing, washing, blixing, washing, bleaching, and washing the color photographic paper in the stabilization bath of this invention, the photographic paper thus processed can be subjected to hightemperature high-speed ferrotype drying directly and without the necessity of predrying. Furthermore, the drying speed of the color photographic paper processed by the process of this invention is higher than that with pretype-drying a photographic paper processed by the aforesaid known development process and dried in a predrying step. Moreover, the color photographic paper thus dried after processing by the process of this invention has superior gloss to the conventionally processed paper. Also, while electrostatic charges are formed even if the color photographic paper processed by the known development processing is dried by ferrotype drying at a low speed, almost no electrostatic charges are formed in drying the color photographic paper processed by the process of this invention.

Still further, because the stabilization bath used in this invention has sufficiently high buffer capacity, satisfactory results can be obtained by conducting the process in any vessel such as a tank, vat, drum, etc. The stabilization bath of this invention is particularly suitable for the continuous processing of a large amount of photographic papers.

Then, the effects of improving the physical properties of color photographic papers, the image stability, and of preventing the stabilization bath from getting musty in using the stabilization process of this invention are shown by the following specific examples although the invention is not limited to these examples by any means. Furthermore, from the examples, it will also become apparent that the objects of this invention are not attained by -using the .polycarboxylic acid or a salt thereof and fhe' wa ter-rsolublezirconium salt individu ally or by using the zirconium salt together with an aldehyde compound, 2,

. EXAMPLE 1 Color Developer pH l0.6

Sodium Metabo rate. 25.0g Sodium Sulfite 2.0g Hydroxylamine (sulfate) 2.0g Potassium Bromide H 0.5g. fi Nitrobenzinidaz ole (nitrate) 0.02g Sodium Hydroxide" 4.0g Benzyl Alcohol l5.8g Diethylene Glycol 20.0ml N-Ethyl-N-/3-(methanesulfoneamidoethyl)- p-phenylenediamine (sulfate) 8.0g Water to make ll Stop-fix Solution pH 4.5

Ammonium Thiosulfat e i: l20.0g Sodium Pyrosu'lfite 200g Glacial Acetic Acid i l0,0g Water to make ll Bleach Solution pH 7.2

Potassium Nitrate 25.0g Potassium Fcrricyanide 20.0g Potassium Bromide 80g Boric Acid 50g Borax 2.5g Water to make ll Hardening-fix Solution pH 95 Ammonium Thiosulfatc 120.0g Sodium Sulfite 5.0g Boric Acid 7 2.5g Formalin (35 40%) 40.0ml

Water to make ll A color photographic paper was prepared by applying to a polyethylene-coated paper a silver bromide emulsion containing a yellow coupler emulsified dispersion, a silver chloride emulsion (silver chloride 70 mol percent) containing a magenta coupler emulsified dispersion, a silver chlorobromide emulsion (silver chloride 70 mol percent) containing a cyan coupler emulsified dispersion, and then a gelatin solution containing a ultraviolet absorbent. The coupler emulsified dispersion used in the preparation of the color photographic paper was prepared by dissolving each coupler in a mixture of dibutyl phthalate and tricresyl phosphate and then dispersing the solution in a gelatin solution in an o/w type using sorbitan monolaurate, Turkey oil, and sodium dodecylbenzenesulfonate as an emulsifying dispersing agent. As the couplers, l-(2',4',6'- trichlorophenyl)-3-[3"(2"',4"'-di-t amylphenoxyacetamido)benzamido]-5-pyrazolone, 2- (2,4-di-tamylphenoxyacetamido)-4,6-dichloro-5- methylphenol, and a-(2methylbenzoyl)-aceto-(2- chloro-S-dodecoxycarbonyl) anilide were used. Also, as the ultraviolet absorbent, the compound described in the specification of Japanese Pat. publication No. 9586/1970 was used. In the emulsion, 2,4-dichloro-6- hydroxy-l ,3,5-triazine---sodium salt was used.

The color photographic paper thus prepared was exposed using i dIor p r iii ter and then subjected to the following colo rgd ev elopment at temperatures lower than 30.0c.-

Color Development 7 minutes Stop-fixing 2 minutes Washing 2 minutes Bleaching 2 minutes Washing 2 minutes Hardening-fix 2 minutes Washing 4 minutes 101 Thereafter, the color photographic paper thus processed was further processed in one of the processing solutions A-F shown in the following table.

Compound A B C D E F Zirconium Oxysulfate 4.0g 4.0g 4.0g 4.0g Citric Acid 3 5g 7.0g 3.5g Tartaric Acid 5 0g 10.0g "Potassium Alum 20.0g

Sodium Metaborate 20.0g Zinc Sulfate 10.0g Water to make ll 11 ll ll ll ll pH 3.5 3.5 3.5 35 3.5 3.5

The adjustment of the pH was conducted using sodium hydroxide.

After the processing, theimage stability was evaluated using the following conditions.

That is to say, the fading percentage of the portion having a density of 1.0 and an increased yellow stain density (AD, l) of the color photographic paper when it was stored for 14 days in the dark at 37.8C and a relative humidity of 90% were measured. The results obtained are shown in the following table.

Also, the fading percentage of the portion of density 1.0 and the increased yellow stain density (AD 2) when the color photographic paper was preserved for 14 days at 60C and a relative humidity of were measured. The results obtained are shown in the following table.

As is clear from the above results shown in the tables, the stabilization baths of this invention (AC) was superior in image stability to the known stabilization baths (DF). Also, when the color photographic papers thus processed were preserved for 7 days at 76.7C (the same condition as the drying step), the color photographic papers processed with the stabilization baths of :known stabilization-bath F stuck to each other but no such phenomenon was observed in the other samples. The test'corresponds to the preserving of color prints in an album for a long period of time, in particular,

this invention showed less in fading of the cyan color under high humidity Conditions image and iess increase in yeiiow Stains as Compared Also, the samples processed'with the known stabilizawith the Color Photographic P p Processed iii the tion bath F became sticky and it was easy to leave finkhowh Stabiiizatioh baths- Furthermore when the gerprints on the samples but no such difficulties were Coior Photographic P p Processed were exposed to encountered with the other samples. an X n n p or a ultraviolet iamp, the increase in y it) From all of the results described above, it is clear that low stains was less in the processing with the stabilizath color hotographic paper processed by the t bifitioh baths of this invention as p r with the P zation bath of this invention after development showed cessing With the known Stabilization bflthsexcellent image stability and physical properties t Then, color photographic papers were prepared using baryta-coated paper as the support in place of the 15 EXAMPLE 2 polyethylene-coated paper using the same manner as v described above. After finishing the above-stated pro- The color photograPhic papcr prepared the h cessings, the color photographic papers were directly manner as Example iywas prhc'essed a subjected to ferrotype drying at 80C without applying coiot deveioper having the sfime mp h as predrying The time required for finishing the drying scribed in Example 1 for 3 minutes-and 30 seconds at procedure in this case is shown in the following table. 3 c and then Phocessed in h bhx bath having the The ferrotype dryer MR 3D made by japo was lowing composition for 1 minute and 30 seconds: used in this step.

Blix Bath Composition Bath A B C D E F Sodium Ferric Ethylenediamine Tetruacctic Acid 50 g m Tetra-acetic Acid, 4 8 g (min) 2.5 2.5 2.5 2.5 3 l0 sulfite g Ammonium Thiosulfatc (6071 aqueous soln.) I50 ml Ammonium Rhodzmidc l5 g As is clear from the above results, the drying period make i I required for drying the photographic papers processed with the stabilization baths AC was almost same as that in the case of the processing with the known stabi- The color photograph? film hh l h for 2 i lization bath E and was shorter than that in the proc'essmes and h processhd a stab'hzmmh bath having ing with the known stabilization bath F. Also, the perthe fohowlhg Composition: iod of time was same as that of the processing with the stabilization bath containing zirconium oxysulfate smibilimion Bmh alone. 40

Then, the electrostatic charges formed on the photo- Zirconium Q Y s I 2 BDZO1C Acid 05;; graphic papers when they were dr ed by ferrotype dry- Citric Acid 35g ing were measured. The results obtained are shown in Additive the following table. The electrostatic meter Statiron-M wif lx zg g fwhhvmg table) I made by Shishida Shokai K. K. was used.

Drying period A B C D E F 3 min. 0lkv 0.1kv O.lkv ()lkv 0.2kv not separated 10 min. 0.1kv ().lkv ().lkv ()rlkv 0.lkv 6.0kv

As is clear from the results in the above table, the amount of electrostatic charges formed in the process- Bath iv Am unt ing with the stabilization baths (A-C) of this invention v G Formaldehyde 5.0g/l was almost same as or less than that of the processing H Acetaidchydc LS /l with the known stabilization baths. Also, the amount i yf y y was the same as that of the processing with the bath 1 tglgs 335: containing zirconium oxysulfate alone. L Acrolein L9 /l Furthermore, the samples thus dried'were humidified H iii for one day at a relative humidlty of 90% and after 0 Methylol diethanolamine 4.5 /l stacking the samples so that the emulsion layers con- P Mcthyiiihydflmmn 8" tacted each other and placing a load of l kg/12cm X 8.3cm on the piled samples, the samples were pre- After the procedures were finis'hed;the samples were served for one day in that condition. In this case, the emulsion layers of the samples processed with the stored in the dark for 14 days'at"37.8fC and"a relative humidity of for 14 days at 60C and 'a relative humidity of 70%, or for 7 days at 76.7C or were exposed to a fluorescent lamp or a xenon lamp. The image stability in these cases was almost same as that in the processing with the stabilization bath A in Example 1. On the other hand, the period of time required for finishing the drying step, the degreeof formation of electrostatic charges, and the sticking state under the condition of REFERENCE EXAMPLE A color photographic paper prepared in the same manner as described in Example lwas processed ina solution having the following composition for 80 seconds at 38C.

Sodium Sulfate 150 g Formaldehyde '10 g Glacial Acetic Acid 1.7 ml Sodium Bromide 2.0 g Succinaldehyde 1.0 g

Water to make Then, the color paper was processed in a hydroxy lamine bath as described in the specificationof US. Pat. No. 3,168,400 for 40 seconds.

Thereafter, after processing the color paper, with the color developer as shown in Example 1 for 7 minutes at 30C, the color paper was processed in the following stop-fix bath for 2 minutes.

Ammonium Thiosulfate (58% aqueous soln.) 215 g Sodium Sulfite 11.2 g Glacial Acetic Acid 20.0 g Sodium Hydroxide 9.0 g Zirconium Oxysulfate 2.12 g Aluminum Sulfate 34.06 g

Water to make Then, the color paper was washed for 2 minutes, processed for 2 minutes in a bleach bath having the same composition as described in Example 1, washed for 2 minutes, processed for 4 minutes in a hardening-fix bath having the same composition as described in Ex ample l, and then washed for 4 minutes.

After drying, the image stability of the color paper was tested as described in Example 1, the results of which showed that the image stability was almost the same as that obtained in omitting the processing with the stabilization bath in Example 1. Also, the various physical properties of the color paper were almost the same as those of the sample which was not processed with the stabilization bath in Example 1. From the above results, it is clear that a stabilization bath containing a water-soluble zirconium salt becomes effective when it is used together with a polycarboxylic acid in accordance with this invention.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What is claimed is:

1. A stabilization process for a color photographic material having silver halide emulsion layers containing color couplers which react with an oxidation product of a color developer to form color images which comprises processing said color photographic material, after developing and bleaching, with a bath having a pH of 2.7 to 4.5 containing (1) a water-soluble zirconium salt and (2) a polycarboxylic acid or a salt thereof, said stabilization process being the final step in a color development process except for rinsing.

2. A stabilization process for a color photographic paper having silver halide emulsion layers containing color'couplers which react with an oxidation product of a color developer to form color images, which process comprises processing said color photographic paper, after developing and bleaching, with a bath having a pH of 2.7 to 4.5 containing a water-soluble zirconium salt and a polycarboxylic acid or a salt thereof, said sta bilization process being the final step in color development process except for rinsing.

3. The stabilization process for a color photographic paper as set forth in claim 2, in which said bath contains 1.2 X 10 to 1.8 X 10' mol/liter of a watersoluble compound having an aldehyde group or 1.0 X 10 to 1.7 X 10 mol/liter of a water-soluble com pound capable of forming formaldehyde, said watersoluble compound having an aldehyde ,group being selected from the group consisting of a monoaldehyde compound represented by the formula (R CHO) wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a carboxyl group, or a heterocyclic ring residue, wherein said R may be a substituted group, when R is a hydrogen atom n is an integer, and when R is a substituent other than a hydrogen atom n is l and a dialdehyde compound represented by the formula OHC (R,),, CHO

wherein R, represents a divalent aliphatic residue, or a divalent aromatic residue, and m is O or 1, said watersoluble compound having a group capable of forming formaldehyde being a compound represented by the formula R crnon wherein R represents an aliphatic residue, an aromatic residue, or a heterocyclic ring residue.

4. The stabilization process for a color photographic paper as set forth in claim 3, in which the amount of said water-soluble dialdehyde compound is 1.0 X 10' to 1.7 X 10 mol/l.

5. The stabilization process for a color photographic paper as set forth in claim 2, in which said polycarboxylic acid is oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, citric acid, glutaric acid, adipic acid, lactic acid, crotonic acid, aconitic acid, itaconic acid, diglycolic acid, citraconic acid, an alkali metal salt of said acid, or an ammonium salt of said acid.

6. The stabilization process for a color photographic paper as set forth in claim 5, in which the amount of the polycarboxylic acid is l to'l5 g/l.

7. The stabilization process for a color photographic paper as set forth in claim 2, in which said watersoluble zirconium salt is zirconium sulfate, zirconium nitrate, zirconium chloride, zirconium oxysulfate, zirconium oxynitrate, or zirconium oxychloride.

8. The stabilization process for a color photographic paper as set forth in claim 7, in which the amount of said water-soluble'zirconium salt is' l to g/l.

9. The stabilization process for a color photographic paper as set forth in claim 2, in which said stabilization bath contains benzoic acid or an alkali metal salt.

10. A stabilization bath for a color photographic paper containing a water-soluble zirconium salt, a polycarboxylic acid, and at least one of a water-soluble compound having an aldehyde group and a watersoluble compound having a group capable of forming formaldehyde.

11. The stabilization bath of claim 10 wherein the bath has a pH of 2.7 to 4.5, the water-soluble compound having an aldehyde group is present in the amount of 1.2 X 10 to 1.8 X 10" mol/liter, the watersoluble compound having a group capable of forming formaldehyde is present in an amount of 1.0 X 10 to 1.7 X 10 mol/liter, said water-soluble compound having an aldehyde group is selected from the group consisting of a monoaldehyde compound represented by the formula (R CH0),

OHC (R,),, CHO

wherein R represents a divalent aliphatic residue, or a divalent aromatic residue, and m is O or 1, said watersoluble compound having a group capable of forming formaldehyde is represented by the formula R CH OH wherein R represents an aliphatic residue, an aromatic residue, or a heterocyclic ring residue. 

1. A STABILIZATION PROCESS FOR COLOR PHOTOGRAPHIC MATERIAL HAVING SILVER HALIDE EMULSION LAYERS CONTAINING COLOR COUPLERS WHICH REACT WITH AN OXIDATION PRODUCT OF A COLOR DEVELOPER TO FORM COLOR IMAGES WHICH COMPRISES PROCESSING SAID COLOR PHOTOGRAPIC MATERIAL, AFTER DEVELOPING AND BLEACHING, WITH A BATH HAVING A PH OF 2.7 TO 4.5 CONTAINING (1) A WATER-SOLUBLE ZIRCONIUM SALT AND (2) A POLYCARBOXYLIC ACID OR SALT THEREOF, SAID STABILIZATION PROCESS BEING THE FINAL IN A COLOR DEVELOPEMEMT PROCESS EXCEPT FOR RINSING.
 2. A stabilization process for a color photographic paper having silver halide emulsion layers containing color couplers which react with an oxidation product of a color developer to form color images, which process comprises processing said color photographic paper, after developing and bleaching, with a bath having a pH of 2.7 to 4.5 containing a water-soluble zirconium salt and a polycarboxylic acid or a salt thereof, said stabilization process being the final step in color development process except for rinsing.
 3. The stabilization process for a color photographic paper as set forth in claim 2, in which said bath contains 1.2 X 10 2 to 1.8 X 10 1 mol/liter of a water-soluble compound having an aldehyde group or 1.0 X 10 2 to 1.7 X 10 1 mol/liter of a water-soluble compound capable of forming formaldehyde, said water-soluble compound having an aldehyde group being selected from the group consisting of a monoaldehyde compound represented by the formula (R - CHO)n wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a carboxyl group, or A heterocyclic ring residue, wherein said R may be a substituted group, when R is a hydrogen atom n is an integer, and when R is a substituent other than a hydrogen atom n is 1 and a dialdehyde compound represented by the formula OHC - (R1)m - CHO wherein R1 represents a divalent aliphatic residue, or a divalent aromatic residue, and m is 0 or 1, said water-soluble compound having a group capable of forming formaldehyde being a compound represented by the formula R2 - CH2OH wherein R2 represents an aliphatic residue, an aromatic residue, or a heterocyclic ring residue.
 4. The stabilization process for a color photographic paper as set forth in claim 3, in which the amount of said water-soluble dialdehyde compound is 1.0 X 10 2 to 1.7 X 10 1 mol/l.
 5. The stabilization process for a color photographic paper as set forth in claim 2, in which said polycarboxylic acid is oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, citric acid, glutaric acid, adipic acid, lactic acid, crotonic acid, aconitic acid, itaconic acid, diglycolic acid, citraconic acid, an alkali metal salt of said acid, or an ammonium salt of said acid.
 6. The stabilization process for a color photographic paper as set forth in claim 5, in which the amount of the polycarboxylic acid is 1 to 15 g/l.
 7. The stabilization process for a color photographic paper as set forth in claim 2, in which said water-soluble zirconium salt is zirconium sulfate, zirconium nitrate, zirconium chloride, zirconium oxysulfate, zirconium oxynitrate, or zirconium oxychloride.
 8. The stabilization process for a color photographic paper as set forth in claim 7, in which the amount of said water-soluble zirconium salt is 1 to 20 g/l.
 9. The stabilization process for a color photographic paper as set forth in claim 2, in which said stabilization bath contains benzoic acid or an alkali metal salt.
 10. A stabilization bath for a color photographic paper containing a water-soluble zirconium salt, a polycarboxylic acid, and at least one of a water-soluble compound having an aldehyde group and a water-soluble compound having a group capable of forming formaldehyde.
 11. The stabilization bath of claim 10 wherein the bath has a pH of 2.7 to 4.5, the water-soluble compound having an aldehyde group is present in the amount of 1.2 X 10 2 to 1.8 X 10 1 mol/liter, the water-soluble compound having a group capable of forming formaldehyde is present in an amount of 1.0 X 10 2 to 1.7 X 10 1 mol/liter, said water-soluble compound having an aldehyde group is selected from the group consisting of a monoaldehyde compound represented by the formula (R - CHO)n wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a carboxyl group, or a heterocyclic ring residue, wherein said R may be a substituted group, when R is a hydrogen atom n is an integer, and when R is a substituent other than a hydrogen atom n is 1 and a dialdehyde compound represented by the formula OHC - (R1)m - CHO wherein R1 represents a divalent aliphatic residue, or a divalent aromatic residue, and m is 0 or 1, said water-soluble compound having a group capable of forming formaldehyde is represented by the formula R2 - CH2OH wherein R2 represents an aliphatic residue, an aromatic residue, or a heterocyclic ring residue. 